JP2018532891A - Electrode-supported tubular solid oxide electrochemical cell - Google Patents

Abstract

An electrode-supported tubular solid oxide electrochemical cell suitable for use in electrochemical chemical synthesis and a method for producing the same are provided.
[Selection] Figure 1

Description

Part of the disclosure of this patent document contains material that is subject to copyright protection. The copyright owner does not object to duplicating either patent documents or patent disclosures by facsimile, as described in the US Patent and Trademark Office patent file or record, but otherwise All rights reserved. The following notice applies to the software and data described below and in the drawings that form part of this document.
"Copyright holder, Low Emission Resources Corporation, 2015. All rights reserved."

  The present disclosure relates to solid state electrochemical cells, and more particularly, electrode-supported tubular solid oxide electrochemical cells for use in electrochemical synthesis of chemicals, and such electrode-supported tubular solid oxide electrochemical cells. The present invention relates to a method of manufacturing a cell.

  Electrochemical cells incorporating ion conducting solid electrolytes are known to be very promising for gas chemical synthesis applications. Electrochemical synthesis using such ion-conducting solid electrolytes can produce high-purity gas at a higher reaction rate and lower cost than conventional catalytic chemical synthesis processes. Without chemical by-products and harmful environmental effects.

For example, the traditional catalyst production of hydrogen gas (H ₂ ) and ammonia (NH ₃ ) and the steps involved in their commercial scale implementation are very energy intensive processes and the greenhouse gas carbon dioxide (CO It is widely recognized by the scientific community around the world that ₂ ) is produced in large quantities and contributes to the warming of the Earth's atmosphere and ocean.

このプロセスは、典型的には高温（例えば、７００−１０００℃）を必要とし、実際には、炭素質原料から硫黄を除去するなどの様々な追加の工程を含む。 Hydrogen gas (H ₂ ) is an important starting material for many industrial chemicals and is also an important source of fuel in renewable energy production. Currently, most industrial hydrogen gas production involves, for example, natural gas, coal, liquefied petroleum gas, etc., for catalytic steam reforming of carbon feedstock as follows:

This process typically requires high temperatures (eg, 700-1000 ° C.) and actually includes various additional steps such as removing sulfur from the carbonaceous feedstock.

Ammonia (NH ₃ ) is one of the world's most abundantly produced inorganic chemicals for many commercial applications, such as chemical fertilizers, explosives, and polymers. Modern commercial production of ammonia typically utilizes several variations of the Haber-Bosch process. In the Haber-Bosch process, gaseous nitrogen (N ₂ ) and hydrogen (H ₂ ) on an iron-based catalyst are reacted and synthesized at high pressure (eg, 150-300 bar) and high temperature (eg, 400-500 ° C.) as follows: Including that.
N ₂ + 3H ₂ → 2NH ₃
In modern ammonia production plants, the nitrogen feed is usually obtained from the atmosphere, but the hydrogen feed is typically obtained from catalytic steam reforming of the carbonaceous feedstock as described above. In practice, the implementation of this process requires various other steps such as separating and purifying the hydrogen before it can be used.

Commercial scale production of industrially important chemicals such as hydrogen and ammonia can be achieved more efficiently and cost-effectively by electrochemical synthesis than traditional catalytic processes as described above. . For example, hydrogen gas can be produced by direct electrolysis of water vapor (H ₂ O) without the need for a carbonaceous source and the corresponding production of carbon dioxide. Ammonia can be produced electrochemically by reacting hydrogen directly with nitrogen, thus eliminating the need for intermediate steps to separate and purify hydrogen prior to use in the synthesis reaction.

  Electrochemical synthesis is generally performed using an electrochemical cell that incorporates two electrodes (anode and cathode) and an electrolyte that separates the two electrodes. As used in electrochemical synthesis applications, the two electrodes are connected to a power source through an electronic circuit, and the electrolyte typically conducts ionic species, but electronic and initial chemical reactants and final chemistry. Non-ionic species such as products are materials that do not conduct. When a voltage is applied between the two electrodes, the reactant dissociates and is ionized at one electrode, and the ionized reactant species moves through the electrolyte toward the counter electrode, where Reacts with a second reactant present at the electrode to form the desired reaction product. Electrode and electrolyte materials and configurations are selected and optimized according to the desired electrochemical synthesis reaction.

  For electrochemical synthesis to be widely applicable and commercially feasible, it is cost-effective and measurable in various configurations, using various materials, depending on the desired electrochemical synthesis reaction There is a need for an electrochemical cell that can be manufactured in a responsive manner. Furthermore, it is desirable that electrochemical cells have structural and chemical stability and durability that can withstand potentially harsh temperatures, pressures and chemical environments in which they may be operated.

  In one aspect, the present disclosure provides a tubular solid oxide electrochemical cell comprising a first porous electrode configured in a tubular shape and a thin layer on at least a portion of the surface of the first porous electrode. An electrolyte disposed as a layer and a second porous electrode disposed on at least a part of the surface of the electrolyte. The first porous electrode includes a first mixed ion / electron conducting composite material comprising a solid oxide electrolyte material and a first electrochemically active metal material. The electrolyte includes a solid oxide electrolyte material. The second porous electrode includes a second mixed ion / electron conducting composite material comprised of the same solid oxide electrolyte material and a second electrochemically active metal material.

  In another aspect, the present disclosure provides a solid tubular solid oxide electrochemical cell. This is made by: That is, the electrode fabric is extruded into a tubular shape to form a first electrode, and the electrode fabric comprises a solid oxide electrolyte material, a first electrochemically active metal material, a carbon-based pore forming material, a binder and a solvent. Containing and extruding the extruded first electrode to burn off the carbon-based pore-forming substance to form pores in the first electrode, and at least part of the surface of the sintered first electrode To form an electrolyte. The electrolyte is a thin layer of solid oxide electrolyte material, and the second electrode is formed on at least a portion of the surface of the electrolyte. The second electrode includes a solid electrolyte material and a second electrochemically active metal material.

  In yet another aspect, the present disclosure provides a process for manufacturing a tubular solid oxide electrochemical cell. The process includes forming an electrode fabric that includes a solid oxide electrolyte material, a first electrochemically active metal material, a first carbon-based pore-forming material, a first binder, and a first solvent. And extruding the electrode fabric into a tubular shape to form a first electrode, and sintering the extruded first electrode. An electrolyte slurry containing a solid oxide electrolyte material and a second solvent is formed and coated on at least a portion of the surface of the sintered first electrode, and the electrolyte coating is sintered. An electrode slurry containing a solid oxide electrolyte material, a second electrochemically active metal material, a second carbon-based pore-forming material, and a third solvent is applied to at least one of the surfaces of the sintered electrolyte. The electrode coating is sintered to form the part.

  For a better understanding of the features, objects and processes included in this disclosure, reference should be made to the detailed description taken in conjunction with the accompanying drawings.

1A, 1B, and 1C are diagrams illustrating a tubular solid oxide electrochemical cell according to an embodiment of the present disclosure.

FIG. 2 shows a flowchart illustrating one embodiment of a process for producing a tubular solid oxide electrochemical cell according to the present disclosure.

  The present disclosure provides for cost effective manufacturing of electrochemical cells that can be customized and optimized for use in electrochemical synthesis, depending on the desired electrochemical synthesis reaction. The electrochemical cell of the present disclosure has a tubular configuration and is made from a solid oxide ceramic material. Tubular solid oxide electrochemical cells according to the present disclosure can be stacked and arranged in various configurations, and commercial scale electrochemical synthesis of various gases such as hydrogen, ammonia, nitric oxide, synthesis gas, etc. Used for mechanical and chemical stability and durability.

  FIG. 1A shows an isometric view of one embodiment of a tubular solid oxide electrochemical cell 100 according to the present disclosure. The electrochemical cell 100 is supported by a first electrode 110 configured in a tubular shape, and an electrolyte 120 and a second electrode 130 are disposed thereon. As shown in FIG. 1A, the electrolyte 120 is disposed as a thin layer on at least a part of the surface of the first electrode 110, and the second electrode 130 is disposed on at least a part of the surface of the electrolyte 120.

FIG. 1B shows a cross-sectional isometric view through the central portion of the tubular solid oxide electrochemical cell 100 shown in FIG. 1A, and FIG. 1C also shows an axial cross-sectional view through a portion of the central portion. The first electrode 110 has an average thickness (T ₁ ), which is the total average thickness (T ₂ ) of the thin layers of the electrolyte 120 and the average thickness (T) of the second electrode 130. _It is thicker than the combination of ₃ ). The relatively thick first electrode provides mechanical support for the electrochemical cell and allows the electrolyte to be thinner, which is the ohmic loss and energy required to transport ions through the electrolyte. Helps reduce both quantities. Typically, the average thickness (T ₁ ) of the first (supporting) electrode is in the range of about 5 mm to about 50 mm, and the average thickness (T ₂ ) of the electrolyte is about 5 microns to about 100 microns. And the average thickness (T ₃ ) of the second electrode is in the range of about 5 microns to about 100 microns.

  1A-1C illustrate an embodiment in which the electrolyte 120 is disposed on the outer surface of the first (supporting) electrode 110 and the second electrode 130 is disposed on the outer surface of the electrolyte 120, the present disclosure In some embodiments, two electrodes are formed on at least a portion of the inner surface of the first electrode and the electrolyte, respectively, and the first (supporting) electrode is the outermost layer of the electrochemical cell.

  Furthermore, depending on the desired electrochemical synthesis reaction, the choice of electrolyte, and the configuration of the reactor, the first (supporting) electrode functions as an anode and the second electrode functions as a cathode or vice versa. (That is, the first (supporting) electrode functions as a cathode and the second electrode functions as an anode).

  The electrolyte used in the electrochemical cell is typically made from a solid oxide electrolyte material such as perovskite, fluorite, and others known in the art. The solid oxide electrolyte material is preferably designed to have high ionic conductivity, low electronic conductivity, and high density to prevent mixing of non-ionized gaseous reactants.

Perovskite generally refers to a class of metal oxide materials having the general formula ABO ₃ , where A refers to a metal cation having a relatively large ionic radius, and B refers to a metal cation having a relatively small ionic radius. . The crystal structure of the perovskite material is very tolerant to vacancy formation, includes a variety of different phases (such as the Aurivirius phase and the Ruddleson Popper phase) and is suitable for use as an ion conducting electrolyte. And “A” is a monovalent metal cation (M ¹⁺ , eg, Na, K), a divalent metal cation (M ²⁺ , eg, Ca, Sr, Ba, Pb), a trivalent metal cation (M ³⁺ , eg, Fe , La, Gd, Y) and combinations thereof, but are not limited to these. “B” is a pentavalent metal cation (M ⁵⁺ , eg, Nb, W), a tetravalent metal cation (M ⁴⁺ , eg, Ce, Zr, Ti), a trivalent metal cation (M ³⁺ , eg, Mn, Fe, Co, Ga) , Al) and combinations thereof, but are not limited to these.

Fluorite generally refers to a class of materials having a face-centered cubic structure and comprising a metal oxide having the general formula MO ₂ , where “M” is a divalent metal cation (M ²⁺ , eg, Ca, Sr , Ba, Mg), trivalent metal cation (M ³⁺ , eg, Sc, Y, Yb, Er, Tm, La, Gd, Dy, Sm, Al, Ga, In), tetravalent metal cation (M ⁴⁺ , eg, Including, but not limited to, Ce, Zr, Th, Hf, Bi) and combinations thereof.

Other metal oxide materials that can be used for the solid oxide electrolyte material according to the present disclosure include pyrochlore (general formula A ₂ B ₂ O ₇ or A _{2 -X} A ′ _X B ₂ O ₆ , where In which A is a trivalent metal cation such as Gd, Sm, La, Nd, Eu, Tb, Bi, Y, Dy, A ′ is a divalent metal cation such as Ca, and B is a tetravalent metal cation such as Ti, Zr, Ru), brown millerite (A ₂ B ₂ O ₅ , where A is a divalent cation, such as Al, Ca, Sr, Ba, and B is a trivalent metal cation, such as Fe, In , Ga, Mn, Cr, Zr, Hf, Ce, Ti) and others.

Depending on the desired electrochemical synthesis reaction, the solid oxide electrolyte material is selected to be a proton (H ⁺ ) conductive material or an oxygen ion (O ²⁻ ) conductive material. The specific composition of the solid oxide electrolyte material and whether it acts as a proton conductor or oxygen ion conductor also determines whether the combination of metal ions (eg, A, A ′, B, or M) is a reactant. And depending on the desired electrochemical synthesis reaction, since it can be manipulated to minimize the chemical reactivity of the electrolyte to reaction conditions and optimize the conductivity of the desired ionic reactive species.

  The first and second electrodes used in the electrochemical cell typically comprise a mixed ion / electron conducting composite of a solid oxide electrolyte material and an electrochemically active material. Furthermore, the first and second electrodes are preferably porous and chemically stable in a highly reducing or oxidizing environment in which the electrochemical cell operates. In some embodiments, the first and second electrodes are made from the same mixed ion / electron conducting composite, and in other embodiments, the first electrode is a first mixed ion / electron conducting composite. Made from a material, the second electrode is made from a second mixed ion / electron conducting composite material that is different from the first mixed ion / electron conducting composite material.

  In prior art electrochemical cells, the electrolyte and electrode typically have different thermal properties, so that when heated, the electrolyte and electrode expand at different rates and crack one or more electrodes. Torn from the electrolyte. When the electrode of the electrochemical cell of the present invention is made of a composite material that incorporates the same solid oxide electrolyte material used for the electrolyte, the coefficient of thermal expansion (CTE) of the electrode material is defined as the CTE of the electrolyte material. It has been found that they can be matched well and prevent cracking and / or tearing observed when heating prior art electrochemical cells. The mixed ion / electron conducting composite used for the electrode typically has at least about 70% by weight of the solid oxide electrolyte material, and preferably about ±± of the thermal expansion coefficient of the solid oxide electrolyte material. It has a coefficient of thermal expansion within 10%.

  When the electrochemical cell is used for an electrochemical synthesis reaction, the electrodes provide reaction sites for the oxidation and reduction half reactions that make up the desired electrochemical synthesis reaction. Thus, the first and second electrodes incorporate an electrochemically active material, which is, for example, a metal or metal oxide or semiconductor material that helps catalyze the desired half-reaction and causes the electrode to conduct electrons. It also provides sex. The electrochemically active material used depends on the desired electrochemical synthesis reaction and is Sc, Ti, Zn, Sr, Y, Zr, Au, Bi, Pb, Co, Pt, Ru, Pd, Ni, Cu , Ag, W, Os, Rh, Ir, Cr, Fe, Mo, V, Re, Mn, Nb, Ta, and oxides, alloys, and mixtures thereof, but are not limited thereto.

  Furthermore, the electrode preferably has a porosity and a microstructure. This allows the reaction gas to travel across the electrode to contact the electrochemical reactant and to dissociate and / or react depending on the desired electrochemical synthesis reaction. The porosity and microstructure of the electrode is provided by incorporating a carbon-based pore former that is baked out of the mixed ion / electron conducting composite during electrode formation, as further described below. The carbon-based pore forming material may include, but is not limited to, graphite powder, starch, powdered and / or granular organic polymer (eg, polymethyl methacrylate, acrylic resin, polyvinyl chloride, etc.). Absent. Depending on the desired electrochemical synthesis reaction, the amount and type of carbon-based pores forming the material can be adjusted to produce an optimal porous microstructure for the electrode.

  FIG. 2 shows a flowchart 200 outlining one embodiment of a method of manufacturing a tubular solid oxide electrochemical cell according to the present disclosure. In general, the first electrode is formed into a tubular shape by extruding the electrode fabric, and the extruded first electrode is sintered before the electrolyte is coated on at least a part of the surface of the first electrode. The After the electrolyte-coated first electrode is sintered, the second electrode is coated on at least a portion of the surface of the electrolyte, and the completed electrochemical cell is heated to sinter the second electrode. The steps involved in this embodiment are described in more detail below.

  The components for the first electrode are mixed at 205 and mixed and ground at 210, typically using a solvent, to adjust the particle size and particle size distribution of the components. Any solvent known and used in the art for grinding can be used, such as water. The components of the first electrode include at least a solid oxide electrolyte material, a first electrochemically active material, and a carbon-based pore forming material. One or more of the other additives described below may be combined with these ingredients, mixed, and milled. After milling to the appropriate particle size and distribution, the mixture of ingredients is dried at 220.

  Binder and solvent are added to the mixture of ingredients at 225 and the resulting mixture is mixed at 230 and aged to form an electrode fabric. The binder may be any known aqueous or non-aqueous binder, such as polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl butyral, acrylic (such as polymethacrylate), polyacrylamide, polyethylene oxide, alginate, cellulose (eg, methylcellulose) , Ethylcellulose, etc.), starch, gum, styrene or binder systems such as Duramax ™ binder (available from The Dow Chemical Company) and combinations and mixtures thereof. The solvent may be any solvent used in ceramic manufacture, such as water, acetone, ethanol, isopropanol, methyl ethyl ketone, α-terpineol, and the like and combinations and mixtures thereof. The choice of binder depends on the other electrode components and solvent. This is because the binder typically must provide wet and dry strength to the electrode fabric and the resulting electrode and be compatible with the solvent.

  One or more other additives known and used in ceramic manufacturing can be added at 225 (if not already added) to allow robustness and smooth extrusion of the electrode fabric. To give other characteristics. Such additives include dispersants such as phosphoric esters of polyacrylic acid, alcohols or phenols (eg available under the Beycostat ™ mark), polymers or polymerization systems such as crosslinkers (eg Bisacrylamide), initiators (eg, ammonium persulfate), and acrylamide with a catalyst (eg, tetramethylethylenediamine), plasticizers such as dioctyl phthalate, viscosity modifiers, flocculants, and lubricants. Can be mentioned. The electrode fabric typically has a solid component of about 30% to about 70% volume, with the remaining volume being solvent.

  After aging, the electrode fabric is extruded through a die at 240 to form a tubular shaped first electrode. Any known extrusion method may be used. The tubular first electrode can be made to any length and diameter, but is typically about 5 cm to about 150 cm long and has an inner diameter of about 0.5 cm to about 5 cm. The extruded tubular first electrode generally has a circular cross-section, but other cross-sectional shapes (eg, semi-circular, elliptical, square, rectangular, triangular, trapezoidal, star-shaped, etc.) are possible and are disclosed herein. Within range. In some embodiments, depending on the particular synthesis reaction and reactor configuration, a non-circular cross-section is effective for packing the cells, dissipating the heat and / or passing through or around the cell or around the cell. Certain advantages, such as reaction flow, can be provided.

  The extruded tubular first electrode is dried at 250 and sintered. During drying and sintering, the extruded tubular first electrode is typically placed horizontally on a holder that prevents bending of the first electrode. The extruded tubular first electrode can be dried at room temperature for up to 48 hours and then sintered to burn off the additive from the extruded tubular electrode. Sintering, for example, gradually heats the extruded tubular electrode at a rate of about 0.1 ° C./min to about 10 ° C./min, more typically about 1 ° C./min to about 2 ° C./min. A set temperature of about 800 ° C. to about 1600 ° C. and hold at the set temperature for up to about 12 hours. In some embodiments, sintering can include gradually heating in stages to one or more intermediate set temperatures and holding at each intermediate set temperature to burn out various different additives. . When the extruded tubular electrode is sintered, especially when the carbon-based pore-forming material is burned out, pores remain in the electrode, so the sintered first electrode is a solid porous cermet (ceramic-metal) composite Become a material.

  The electrolyte may be layered at 260, for example, by spray coating, dip coating or other methods, as a thin layer on at least a portion of the surface of the sintered first electrode. Formed by. The electrolyte may be formed on a part of the inner surface or the outer surface of the sintered first electrode. The electrolyte slurry is a solid oxide electrolyte material that is a solvent (as described above) and optionally one or more other additives commonly used in ceramic manufacturing (such as the binder, dispersant, polymer, etc. described above). ), Mixing and grinding, and then adding more solvent to form a robust slurry that is coated or laminated on the first electrode. The electrolyte slurry typically contains about 10% to about 30% volume of solid components, with the remaining volume being solvent. Next, at 270, the electrolyte is dried and sintered to form a solid electrolyte layer.

  The second electrode is formed at 280, for example, by spray coating, dip coating or other layering of electrode slurry (formed of 275) on at least a portion of the surface of the sintered electrolyte. Is done. The electrode slurry comprises a solid oxide electrolyte material, a second electrochemically active material, and a carbon-based pore-forming material, a solvent (eg, as described above) and, optionally, common in ceramic production One or more other additives used (such as binders, dispersants, polymers, etc. as described above) are combined, mixed and milled, then further solvent is added to coat or layer on the electrolyte It can be formed by forming a slurry having a fastness. The electrode slurry typically contains about 10% to about 30% volume of solid components, with the remaining volume being solvent. The second electrode is then dried and sintered at 290 as described above to form a solid porous second electrode.

  The operations described herein may be performed in any order unless otherwise specified, and embodiments of the present disclosure include more or fewer operations than those disclosed herein. Please understand that you get.

  It will be further understood that the articles “a”, “an”, “the” and “said” are intended to mean that one or more elements or steps may be present. The terms “comprising”, “including” and “having” are intended to be inclusive and there may be additional elements or steps other than those explicitly listed. Means that.

  The foregoing description has been presented for the purpose of describing particular aspects of the disclosure and is not intended to limit the disclosure. Those skilled in the relevant art will appreciate that many additions, modifications, variations and improvements can be made in light of the above teachings and still be within the scope of this disclosure.

Claims (29)

A tubular solid oxide electrochemical cell,
A first porous electrode configured in a tubular shape and including a first mixed ion / electron conductive composite material comprising a solid oxide electrolyte material and a first electrochemically active material When,
An electrolyte disposed as a thin layer on at least a portion of the surface of the first porous electrode and comprising the solid oxide electrolyte material;
A second mixed ion / electron conductive composite material comprising a second porous electrode disposed on at least a part of the surface of the electrolyte, and comprising the solid oxide electrolyte material and a second electrochemically active material A tubular solid oxide electrochemical cell comprising: a second porous electrode comprising:   2. The tubular solid oxide electrochemical cell according to claim 1, wherein the solid oxide electrolyte material includes a proton conducting material.   The tubular solid oxide electrochemical cell according to claim 1, wherein the solid oxide electrolyte material includes an oxygen ion conducting material.   2. The tubular solid oxide electrochemical cell according to claim 1, wherein the solid oxide electrolyte material comprises a material selected from the group consisting of perovskite, fluorite, pyrochlore and brown milllite. . 2. The tubular solid oxide electrochemical cell of claim 1 wherein the solid oxide electrolyte material comprises a perovskite material having the general formula ABO ₃ wherein A is a monovalent, divalent and trivalent metal. A tubular solid oxide electrochemical cell selected from the group consisting of cations and combinations thereof, wherein B is selected from the group consisting of pentavalent, tetravalent and trivalent metal cations and combinations thereof. In tubular solid oxide electrochemical cell of claim 1, wherein the solid oxide electrolyte material comprises a fluorite materials having the general formula MO _2, in the formula, M is a divalent or trivalent metal cation and A tubular solid oxide electrochemical cell selected from the group consisting of combinations thereof.   The tubular solid oxide electrochemical cell of claim 1, wherein the first porous electrode comprises at least about 70% by weight of the solid oxide electrolyte material.   The tubular solid oxide electrochemical cell according to claim 1, wherein the first electrochemically active material is Sc, Ti, Zn, Sr, Y, Zr, Au, Bi, Pb, Co, Pt, Ru, Pd, Tubular solid selected from the group consisting of Ni, Cu, Ag, W, Os, Rh, Ir, Cr, Fe, Mo, V, Re, Mn, Nb, Ta and their oxides, alloys, and combinations thereof Oxide type electrochemical cell.   The tubular solid oxide electrochemical cell of claim 1, wherein the second porous electrode comprises at least about 70% by weight of the solid oxide electrolyte material.   The tubular solid oxide electrochemical cell according to claim 1, wherein the second electrochemically active material is Sc, Ti, Zn, Sr, Y, Zr, Au, Bi, Pb, Co, Pt, Ru, Pd, Tubular solid selected from the group consisting of Ni, Cu, Ag, W, Os, Rh, Ir, Cr, Fe, Mo, V, Re, Mn, Nb, Ta and their oxides, alloys, and combinations thereof Oxide type electrochemical cell.   2. The tubular solid oxide electrochemical cell of claim 1 wherein the first mixed ion / electron conducting composite material and the second mixed ion / electron conducting composite material are the same. .   The tubular solid oxide electrochemical cell of claim 1, wherein the first porous electrode has an average thickness in the range of about 5 mm to about 50 mm.   The tubular solid oxide electrochemical cell of claim 1, wherein the thin layer of electrolyte has an average thickness in the range of about 5 microns to about 100 microns.   The tubular solid oxide electrochemical cell of claim 1, wherein the second porous electrode has an average thickness in the range of about 5 microns to about 100 microns.   2. The tubular solid oxide electrochemical cell of claim 1, wherein the tubular shape has a cross-sectional shape selected from the group consisting of a circle, a semicircle, an ellipse, a square, a rectangle, a trapezoid, a triangle, and a star. Oxide type electrochemical cell.   2. The tubular solid oxide electrochemical cell according to claim 1, wherein each of the first mixed ion / electron conductive composite material and the second mixed ion / electron conductive composite material is a thermal expansion of the solid oxide electrolyte. A tubular solid oxide electrochemical cell having a coefficient of thermal expansion within about 10% of the coefficient. Tubular solid oxide electrochemical cell, the tubular solid oxide electrochemical cell
Extruding the electrode fabric into a tubular shape to form a first electrode, the electrode fabric comprising a solid oxide electrolyte material, a first electrochemically active material, a carbon-based pore-forming material, a binder and a solvent; ,
Sintering the extruded first electrode to burn off the carbon-based pore-forming material to form a plurality of pores in the first electrode;
Forming an electrolyte on at least a portion of the surface of the sintered first electrode, the electrolyte including a thin layer of the solid oxide electrolyte material;
A second electrode is formed on at least a portion of the surface of the electrolyte, and the second electrode is manufactured by a method including a step including the solid oxide electrolyte material and a second electrochemically active material. Tubular solid oxide electrochemical cell.   The tubular solid oxide electrochemical cell of claim 17, wherein the first electrochemically active material and the second electrochemically active material are the same. The tubular solid oxide electrochemical cell of claim 17, wherein forming the electrolyte comprises:
Coating at least a portion of the surface of the sintered first electrode with an electrolyte slurry, the electrolyte slurry comprising the solid oxide electrolyte material and a second solvent;
A tubular solid oxide electrochemical cell comprising drying and sintering a coated electrolyte. The tubular solid oxide electrochemical cell of claim 17, wherein forming the second electrode comprises:
At least a portion of the surface of the electrolyte is coated with an electrode slurry, the electrode slurry comprising the solid oxide electrolyte material, a second electrochemically active material, a second carbon-based pore-forming material, and a third A solvent of
Tubular solid oxide type electricity comprising drying and sintering the coated second electrode to burn away the second carbon-based pore-forming material to form a plurality of pores in the second electrode Chemical cell. A method for producing a tubular solid oxide electrochemical cell comprising:
Forming an electrode fabric comprising a solid oxide electrolyte material, a first electrochemically active material, a first carbon-based pore-forming material, a first binder and a first solvent;
Extruding the electrode fabric into a tubular shape to form a first electrode;
Sintering the extruded first electrode;
Forming an electrolyte slurry comprising the solid oxide electrolyte material and a second solvent;
Coating the electrolyte slurry on at least a portion of the surface of the sintered first electrode;
Sintering the electrolyte coating,
Forming an electrode slurry comprising the solid oxide electrolyte material, the second electrochemically active material, the second carbon-based pore-forming material, and a third solvent;
Coating the electrode slurry on at least a portion of the surface of the sintered electrolyte; and
Sintering the electrode coating. The method of claim 21, wherein forming the electrode fabric comprises
Mixing and crushing the solid oxide electrolyte material, the first electrochemically active material, and the first carbon-based pore-forming material to form a pulverized mixture of components;
Drying the ground mixture of the ingredients,
Adding a first binder and a first solvent to the milled mixture of the dried ingredients.   The method of claim 21, wherein the electrode fabric is at least selected from the group consisting of a dispersant, a polymer, a cross-linking agent, an initiator, a catalyst, a plasticizer, a viscosity modifier, a flocculent, and a lubricant. A method further comprising one component.   24. The method of claim 21, wherein the electrode fabric comprises about 30% to about 70% by volume of a solid component. The method of claim 21, wherein sintering the extruded first electrode comprises:
Gradually heating to a set temperature between about 800 ° C. and about 1600 ° C .; and
Holding at the set temperature for up to about 12 hours.   24. The method of claim 21, wherein the electrolyte slurry further comprises at least one component selected from the group consisting of a second binder, a dispersant, a polymer, a crosslinker, an initiator, a catalyst, and a plasticizer.   24. The method of claim 21, wherein the electrolyte slurry comprises about 10% to about 30% by volume of a solid component.   24. The method of claim 21, wherein the electrode slurry further comprises at least one component selected from the group consisting of a dispersant, a polymer, a crosslinker, an initiator, a catalyst, and a plasticizer.   24. The method of claim 21, wherein the electrode slurry comprises about 10% to about 30% by volume of a solid component.

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